CN104086882A - Application of needle-like wollastonite served as polypropylene cold-resistant agent and cold-resistant polypropylene material containing needle-like wollastonite - Google Patents

Application of needle-like wollastonite served as polypropylene cold-resistant agent and cold-resistant polypropylene material containing needle-like wollastonite Download PDF

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CN104086882A
CN104086882A CN201410314226.9A CN201410314226A CN104086882A CN 104086882 A CN104086882 A CN 104086882A CN 201410314226 A CN201410314226 A CN 201410314226A CN 104086882 A CN104086882 A CN 104086882A
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polypropylene
cold
wollastonite
resistant
acicular wollastonite
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CN104086882B (en
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杨桂生
俞飞
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Hefei Genius New Materials Co Ltd
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Hefei Genius New Materials Co Ltd
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00Use of ingredients characterised by shape
    • C08K7/02Fibres or whiskers
    • C08K7/04Fibres or whiskers inorganic
    • C08K7/10Silicon-containing compounds
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/12Polypropene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/003Additives being defined by their diameter
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/016Additives defined by their aspect ratio

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Abstract

The invention provides an application of needle-like wollastonite served as a polypropylene cold-resistant agent. Needle-like wollastonite is modified needle-like wollastonite which is subjected to surface treatment by a titanate coupling agent and has a length-diameter ratio of (7:1)-(22:1). The invention also discloses a cold-resistant polypropylene material containing needle-like wollastonite. Needle-like wollastonite can be used for significantly improving the low-temperature toughness retention rate of the polypropylene material, and can be used for ensuring that the low-temperature toughness retention rate of the polypropylene material at -30DEG C reaches more than 50%. The additive amount of needle-like wollastonite accounts for 0.5-1.5% of the mass of polypropylene in percentage by weight, thus the condition that the conventional needle-like wollastonite is used as a polypropylene filling material is broken, and the usage amount of needle-like wollastonite is much less than that of needle-like wollastonite served as the filling material.

Description

A kind of acicular wollastonite is as the purposes of polypropylene cold-resistant agent and the cold-resistant polypropylene material that contains this acicular wollastonite
 
Technical field
The present invention relates to polymer modification field, relate in particular to a kind of acicular wollastonite as the purposes of polypropylene cold-resistant agent and the cold-resistant polypropylene material that contains this acicular wollastonite.
 
Background technology
Along with the development of modern science and technology, people are more and more higher to the requirement of material property, especially to general-purpose plastics polypropylene material.Polypropylene is mainly used in the fields such as automobile, household electrical appliances, tubing, medical treatment, food.Because the low-temperature flexibility of polypropylene material is poor, if just need to carry out toughening modifying to improve the low-temperature flexibility of polypropylene material to it for low temperature environment, the common material that improves polypropylene low temperature toughness is terpolymer EP rubber (EPDM), based elastomers (POE), SBS elastomer (SBS), hydrogenated styrene-butadiene-styrene elastomerics (SEBS), and its consumption is generally the 10wt% ~ 40wt% of polypropylene quality.As: Chinese patent CN 1221607C utilizes SEBS tenacity-increased profax; Chinese patent CN 102311584 B, CN 102675745 A, CN 102516663 A utilize POE tenacity-increased profax; Chinese patent CN 1119374 C utilize EPDM and SBS tenacity-increased profax.
Acicular wollastonite is mainly used for polyacrylic filling to strengthen, reduce costs at present, and the modulus of polypropylene material and thermal distortion are increased, and the consumption of general acicular wollastonite is 5% ~ 50% of polypropylene quality.As: Chinese patent CN 103059415 A be exactly wherein using acicular wollastonite as filling, falling original use, and its consumption are high, is equivalent to the polyacrylic umber of matrix resin; Chinese patent CN 102161820 A, using acicular wollastonite as weighting material reinforced polycarbonate, and consumption accounts for 5% ~ 20% of whole composition.So, set it as the concept of polypropylene cold-resistant agent, before the present invention, do not occur.The present invention first cold-resistant agent using acicular wollastonite as polypropylene material uses, and can obviously improve the low-temperature flexibility of polypropylene material.And consumption is generally the 0.5wt% ~ 1.5wt% of polypropylene quality, this and traditional acicular wollastonite differ greatly as filling toughener consumption, and compared with traditional polypropylene toughening agent (POE, EPDM etc.), addition is less.
 
Summary of the invention
The invention provides a kind of acicular wollastonite as the purposes of polypropylene cold-resistant agent and the cold-resistant polypropylene material that contains this acicular wollastonite, the present invention proposes to use acicular wollastonite as polypropylene cold-resistant agent first, can partially or completely substitute traditional polypropylene toughening agent, polyacrylic low-temperature flexibility conservation rate is had to significant effect.
Technical scheme of the present invention is as follows:
Acicular wollastonite is as a purposes for polypropylene cold-resistant agent, and described acicular wollastonite is for carrying out the modified acicular wollastonite that surface treatment, length-to-diameter ratio are 7:1 ~ 22:1 through titanate coupling agent.
Further, described titanate coupling agent is sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester (NDZ-201).
The particle diameter of described modified acicular wollastonite is 600 ~ 1250 orders.
Another object of the present invention is to provide a kind of cold-resistant polypropylene material containing acicular wollastonite, comprises polypropylene and above-mentioned modified acicular wollastonite, and the consumption of described modified acicular wollastonite is 0.5 ~ 1.5% of polypropylene weight.
Further, described polypropylene is homo-polypropylene.
Also comprise 0.2 ~ 0.5% oxidation inhibitor, 0.1 ~ 0.3% lubricant and the steady agent of 0.1 ~ 0.3% light that account for respectively polypropylene weight.
Described oxidation inhibitor is the compound of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (anti-1010) and three [2,4-di-tert-butyl-phenyl] phosphorous acid ester (anti-168); Described lubricant is ethylene bis stearamide (EBS); The steady agent of described light is 50% hindered amine as light stabilizer 2,2,6,6-tetramethyl--4-low polypropylene miser of piperidine alcohols stearate (UV-3853PP5) and 2-(2-hydroxyl-uncle 5-good fortune base phenyl) compound of benzotriazole (UV-5411).
Described cold-resistant polypropylene material also comprises 10 ~ 40% the toughner that accounts for polypropylene weight, and described toughner is terpolymer EP rubber (EPDM), based elastomers (POE), SBS elastomer (SBS) or hydrogenated styrene-butadiene-styrene elastomerics (SEBS).
Usefulness of the present invention:
1, the present invention uses acicular wollastonite as polypropylene cold-resistant agent, particularly the maintenance of homo-polypropylene low-temperature flexibility is had to significant effect.
2,, by acicular wollastonite and the traditional composite use of polypropylene toughening agent, it keeps effect better than both respectively independent results of use to polypropylene low temperature toughness.
3, acicular wollastonite usage quantity of the present invention is less, and generally its consumption is 0.5% ~ 1.5wt% of polypropylene quality, broken that traditional acicular wollastonite fills as polypropylene that material uses and consumption to be also compared to the amount that stopping composition uses little a lot.
4, widened the use range of acicular wollastonite, broken acicular wollastonite in the past and filled, reduce costs use mainly as polyacrylic enhancing.
 
Embodiment
Below in conjunction with some embodiment and comparative example, the invention will be further described.
The material of using in embodiment and comparative example has:
Homo-polypropylene S1003 Shanghai match section;
Homo-polypropylene K1885 China Petrochemical Industry Yanshan Petrochemical;
Homo-polypropylene HI828 Korea S Samsung;
Homo-polypropylene HX3900 Korea S SK;
Acicular wollastonite A model: 1250 orders (length-to-diameter ratio 7:1, particle diameter 1250 orders) Liaoning celestial stone mining industry company limited;
Acicular wollastonite B model: G-80(length-to-diameter ratio 15:1, particle diameter 800 orders) Liaoning celestial stone mining industry company limited;
Acicular wollastonite C model: F-90(length-to-diameter ratio 22:1, particle diameter 600 orders) Liaoning celestial stone mining industry company limited;
Oxidation inhibitor A Irganox1010 Switzerland Ciba;
Oxidation inhibitor B Irganox168 Switzerland Ciba;
Chaoyang Chemical Co., Ltd. of Lubricate EBS Indonesia;
The steady agent A of light UV-3853PP5 U.S. cyanogen spy;
The steady agent B of light UV-5411 U.S. cyanogen spy;
Toughner A POE ENGAGE8842 LG-DOW;
Toughner B POE LC670 Korea S LG.
Carry out GB/T 1843 with Analysis of A Cantilever Beam Under notched Izod impact strength.
The listed embodiment of the present invention is exemplary embodiments of the present invention, and so protection scope of the present invention is not limited to this.
Note: low-temperature flexibility conservation rate=(shock strength/23 of 30 DEG C DEG C shock strength) * 100%.
The modification of acicular wollastonite is in acicular wollastonite, to add to account for total mass 1% titanate coupling agent (NDZ-201) and carry out surface treatment gained.Process gained by the acicular wollastonite of 1% coupling agent NDZ-201 and 99%.Concrete processing mode is as follows: first take the acicular wollastonite of 99 mass parts in high-speed mixer, the coupling agent NDZ-201 that then takes 1 mass parts slowly adds and starts mixing machine from the upper end aperture of high-speed mixer and is mixed to get modified acicular wollastonite.
 
embodiment 1
Be 100 parts of polypropylene S1003 by weight part, modified acicular wollastonite 1250 orders of 0.5 part, the anti-oxidant Irganox 1010 of 0.1 part, the anti-oxidant Irganox 168 of 0.1 part, the Lubricate EBS of 0.1 part, the steady agent UV-3853PP5 of light of 0.05 part, the steady agent UV-5411 of light of 0.05 part is after high mixer mixes, through twin screw extruder extruding pelletization.Then be injection molded into standard batten with single screw injection molding machine, be to place at least 24 hours under 23 DEG C ± 2 DEG C and the humidity condition that is RH50% ± 5% in temperature, carry out the socle girder notch shock test under normal temperature and low-temperature condition, its cold condition is :-30 DEG C, 3 hours again.Test result is in Table-1.
embodiment 2
Be the polypropylene K1885 of 100 parts by weight part, the modified acicular wollastonite G-80 of 1.5 parts, the anti-oxidant Irganox 1010 of 0.2 part, the anti-oxidant Irganox 168 of 0.3 part, the Lubricate EBS of 0.3 part, the steady agent UV-3853PP5 of light of 0.2 part, the steady agent UV-5411 of light of 0.1 part is after high mixer mixes, through twin screw extruder extruding pelletization.Then be injection molded into standard batten with single screw injection molding machine, be to place at least 24 hours under 23 DEG C ± 2 DEG C and the humidity condition that is RH50% ± 5% in temperature, carry out the socle girder notch shock test under normal temperature and low-temperature condition, its cold condition is :-30 DEG C, 3 hours again.Test result is in Table-1.
embodiment 3
Be the polypropylene HI828 of 100 parts by weight part, the modified acicular wollastonite F-90 of 1.0 parts, the anti-oxidant Irganox 1010 of 0.2 part, the anti-oxidant Irganox 168 of 0.2 part, the Lubricate EBS of 0.2 part, the steady agent UV-3853PP5 of light of 0.15 part, the steady agent UV-5411 of light of 0.1 part is after high mixer mixes, through twin screw extruder extruding pelletization.Then be injection molded into standard batten with single screw injection molding machine, be to place at least 24 hours under 23 DEG C ± 2 DEG C and the humidity condition that is RH50% ± 5% in temperature, carry out the socle girder notch shock test under normal temperature and low-temperature condition, its cold condition is :-30 DEG C, 3 hours again.Test result is in Table-1.
comparative example 1
Be the polypropylene S1003 of 100 parts by weight part, the anti-oxidant Irganox 1010 of 0.1 part, the anti-oxidant Irganox 168 of 0.1 part, the Lubricate EBS of 0.1 part, the steady agent UV-3853PP5 of light of 0.05 part, the steady agent UV-5411 of light of 0.05 part is after high mixer mixes, through twin screw extruder extruding pelletization.Then be injection molded into standard batten with single screw injection molding machine, be to place at least 24 hours under 23 DEG C ± 2 DEG C and the humidity condition that is RH50% ± 5% in temperature, carry out the socle girder notch shock test under normal temperature and low-temperature condition, its cold condition is :-30 DEG C, 3 hours again.Test result is in Table-1.
comparative example 2
Be the polypropylene K1885 of 100 parts by weight part, the anti-oxidant Irganox 1010 of 0.2 part, the anti-oxidant Irganox 168 of 0.3 part, the Lubricate EBS of 0.3 part, the steady agent UV-3853PP5 of light of 0.2 part, the steady agent UV-5411 of light of 0.1 part is after high mixer mixes, through twin screw extruder extruding pelletization.Then be injection molded into standard batten with single screw injection molding machine, be to place at least 24 hours under 23 DEG C ± 2 DEG C and the humidity condition that is RH50% ± 5% in temperature, carry out the socle girder notch shock test under normal temperature and low-temperature condition, its cold condition is :-30 DEG C, 3 hours again.Test result is in Table-1.
comparative example 3
Be the polypropylene HI828 of 100 parts by weight part, the anti-oxidant Irganox 1010 of 0.2 part, the anti-oxidant Irganox 168 of 0.2 part, the Lubricate EBS of 0.2 part, the steady agent UV-3853PP5 of light of 0.15 part, the steady agent UV-5411 of light of 0.1 part is after high mixer mixes, through twin screw extruder extruding pelletization.Then be injection molded into standard batten with single screw injection molding machine, be to place at least 24 hours under 23 DEG C ± 2 DEG C and the humidity condition that is RH50% ± 5% in temperature, carry out the socle girder notch shock test under normal temperature and low-temperature condition, its cold condition is :-30 DEG C, 3 hours again.Test result is in Table-1.
Can find out from the performance comparison of upper table embodiment 1 ~ 3 and comparative example 1 ~ 3, the present invention adds low-temperature flexibility conservation rate that modified acicular wollastonite can make polypropylene material as cold-resistant agent more than 50%, and does not add polypropylene material low-temperature flexibility conservation rate in the comparative example 1-3 of acicular wollastonite cold-resistant agent less than 30%.
embodiment 4
Be the polypropylene HX3900 of 100 parts by weight part, modified acicular wollastonite 1250 orders of 1.0 parts, the anti-oxidant Irganox 1010 of 0.2 part, the anti-oxidant Irganox 168 of 0.2 part, the Lubricate EBS of 0.25 part, the steady agent UV-3853PP5 of light of 0.15 part, the steady agent UV-5411 of light of 0.15 part is after high mixer mixes, through twin screw extruder extruding pelletization.Then be injection molded into standard batten with single screw injection molding machine, be to place at least 24 hours under 23 DEG C ± 2 DEG C and the humidity condition that is RH50% ± 5% in temperature, carry out the socle girder notch shock test under normal temperature and low-temperature condition, its cold condition is :-30 DEG C, 3 hours again.Test result is in Table-2.
embodiment 5
Be the polypropylene HX3900 of 100 parts by weight part, the toughner POE ENGAGE8842 of 10 parts, modified acicular wollastonite 1250 orders of 1.0 parts, the anti-oxidant Irganox 1010 of 0.2 part, the Lubricate EBS of 168,0.25 parts of the anti-oxidant Irganox of 0.2 part, the steady agent UV-3853PP5 of light of 0.15 part, the steady agent UV-5411 of light of 0.15 part is after high mixer mixes, through twin screw extruder extruding pelletization.Then be injection molded into standard batten with single screw injection molding machine, be to place at least 24 hours under 23 DEG C ± 2 DEG C and the humidity condition that is RH50% ± 5% in temperature, carry out the socle girder notch shock test under normal temperature and low-temperature condition, its cold condition is :-30 DEG C, 3 hours again.Test result is in Table-2.
embodiment 6
Be the polypropylene HX3900 of 100 parts by weight part, the toughner POE LC670 of 40 parts, the modified acicular wollastonite G-80 of 1.0 parts, the anti-oxidant Irganox 1010 of 0.2 part, the Lubricate EBS of 168,0.25 parts of the anti-oxidant Irganox of 0.2 part, the steady agent UV-3853PP5 of light of 0.15 part, the steady agent UV-5411 of light of 0.15 part is after high mixer mixes, through twin screw extruder extruding pelletization.Then be injection molded into standard batten with single screw injection molding machine, be to place at least 24 hours under 23 DEG C ± 2 DEG C and the humidity condition that is RH50% ± 5% in temperature, carry out the socle girder notch shock test under normal temperature and low-temperature condition, its cold condition is :-30 DEG C, 3 hours again.Test result is in Table-2.
comparative example 4
Be the polypropylene HX3900 of 100 parts by weight part, the toughner POE ENGAGE8842 of 10 parts, the anti-oxidant Irganox 1010 of 0.2 part, the anti-oxidant Irganox 168 of 0.2 part, the Lubricate EBS of 0.25 part, the steady agent UV-3853PP5 of light of 0.15 part, the steady agent UV-5411 of light of 0.15 part is after high mixer mixes, through twin screw extruder extruding pelletization.Then be injection molded into standard batten with single screw injection molding machine, be to place at least 24 hours under 23 DEG C ± 2 DEG C and the humidity condition that is RH50% ± 5% in temperature, carry out the socle girder notch shock test under normal temperature and low-temperature condition, its cold condition is :-30 DEG C, 3 hours again.Test result is in Table-2.
Can find out from above embodiment 4 ~ 6 and comparative example 4, traditional toughner POE is to polyacrylic toughening effect compared with modified acicular wollastonite cold-resistant agent of the present invention, and under its normal temperature, toughening effect and the present invention are suitable; But under condition, the polypropylene toughness conservation rate of comparative example 4 is 50.1% at low temperatures, significantly lower than the low-temperature flexibility conservation rate of embodiment of the present invention 4-6.
In addition, in embodiment 5-6 by traditional toughner and the composite use of modified acicular wollastonite cold-resistant agent of the present invention, its effect is all better than the effect of the embodiment of both independent uses 4, comparative example 4, and its low-temperature flexibility conservation rate can reach more than 60%, low temperature socle girder notch shock also exceeds more than one times.

Claims (8)

1. acicular wollastonite, as a purposes for polypropylene cold-resistant agent, is characterized in that: described acicular wollastonite is for carrying out the modified acicular wollastonite that surface treatment, length-to-diameter ratio are 7:1 ~ 22:1 through titanate coupling agent.
2. acicular wollastonite, as the purposes of polypropylene cold-resistant agent, is characterized in that according to claim 1: described titanate coupling agent is sec.-propyl three (dioctylphyrophosphoric acid acyloxy) titanic acid ester.
3. acicular wollastonite, as the purposes of polypropylene cold-resistant agent, is characterized in that according to claim 1: the particle diameter of described modified acicular wollastonite is 600 ~ 1250 orders.
4. the cold-resistant polypropylene material containing acicular wollastonite, it is characterized in that: described cold-resistant polypropylene material comprises the modified acicular wollastonite described in polypropylene and the claims 1-3 any one, and the consumption of described modified acicular wollastonite is 0.5 ~ 1.5% of polypropylene weight.
5. cold-resistant polypropylene material according to claim 4, is characterized in that: described polypropylene is homo-polypropylene.
6. cold-resistant polypropylene material according to claim 4, is characterized in that: described cold-resistant polypropylene material also comprises 0.2 ~ 0.5% oxidation inhibitor, 0.1 ~ 0.3% lubricant and the steady agent of 0.1 ~ 0.3% light that account for respectively polypropylene weight.
7. cold-resistant polypropylene material according to claim 6, is characterized in that: described oxidation inhibitor is the compound of four [β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester and three [2,4-di-tert-butyl-phenyl] phosphorous acid ester; Described lubricant is ethylene bis stearamide; The steady agent of described light is 50% hindered amine as light stabilizer 2,2,6,6-tetramethyl--4-low polypropylene miser of piperidine alcohols stearate and 2-(2-hydroxyl-uncle 5-good fortune base phenyl) compound of benzotriazole.
8. cold-resistant polypropylene material according to claim 4, it is characterized in that: described cold-resistant polypropylene material also comprises 10 ~ 40% the toughner that accounts for polypropylene weight, and described toughner is terpolymer EP rubber, based elastomers, SBS elastomer or hydrogenated styrene-butadiene-styrene elastomerics.
CN201410314226.9A 2014-07-03 2014-07-03 A kind of cold-resistant polypropylene material of the acicular wollastonite as the purposes of Polypropylene cold-resistant agent and containing the acicular wollastonite Active CN104086882B (en)

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CN106566072A (en) * 2016-10-21 2017-04-19 广西师范学院 Modified polypropylene composite material and preparation method thereof
CN106750977A (en) * 2017-01-19 2017-05-31 冯云 A kind of bumper cold-resistant anti-freezing type shape memory polypropylene material and preparation method thereof
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